A 2D Wavy Parquet Architecture Based on the Biphenyl-3,3',4,4'-tetracarboxylic Acid and Bis(2-benzimidazole)alkanes Ligands

A double-T-shaped ligand （H4BPTC） and bis（2-benzimidazole）alkanes as the spacers have been firstly used to direct the assembly of a 2D coordination polymer with wavy parquet network topology, [Zn（BPTC）0.5（H2C2EIm）（H2O）]n （1, C24H18ZnN4O5, Mr = 507.79, H4BPTC = biphenyl-3,3＇,4,4＇-tetracarboxylic acid, H2C2EIm = 2,2＇-（1,2-ethanediyl）-bis（1H-benzi- midazole）, which was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/n with a = 1.1844（5）, b = 1.4019（5）, c = 1.4026（5） nm, β = 108.359（5）°, V = 2.2104（15） nm3, Z = 4, Dc = 1.526 g/cm3, μ（MoKα） = 1.156 mm-1, F（000） = 1040, S = 1.038, the final R = 0.0427 and wR = 0.0793 for 3834 reflections with I 2σ（I）. The compound units are linked through BPTC ligands into a wavilness parquet 2D layer and further connected into a 3D framework via π-π packing interactions between the adjacent H2C2EIm ligands and weak N-H…O hydrogen bonding between uncoordinated carboxylate and the nitrogen atoms of H2C2EIm as well as the free water molecules.

Controlled Self-assembly of Two Coordination Polymers via subtly Varying Bis(2-methyl imidazole) Ligands:from 3-Connected(6,3) Net to 4-Connected sql Net

Two coordination polymers constructed from 3,4-thiophenedicarboxylic acid and bis（2-methyl imidazole） ligands, namely, {[Cd2（tdc）2（bip）2]·7H20}n （1） and [Cd（tdc）（bib）]n （2） （Hgtdc = 3,4-thiophenedicarboxylic acid, bip = 1,3-bis-（imidazol-2-methyl）propane and bib = 1,4-bis（imidazol-2-methyl）butane）, have been synthesized and structurally characterized by single-crystal X-ray diffraction. Structural analyses reveal that 1 exhibits a two-dimensional （2D） layered network with 3-connected （6,3） topology, which is further connected into a three- dimensional （3D） supramolecular structure by intermolecular hydrogen bonds. However, 2 features a 2D network which can be rationalized as a 4-connected sql net. The results indicate the subtle difference of auxiliary bis（imidazol-2-methyl） ligands may lead to diverse architectures. Moreover, they exhibit luminescence emission in the solid state at room temperature.

Flexible Bis(benzimidazole)-based Ligands Directed the Structure Characteristics of Coordination Polymers Based on Diphenic Acid Co-ligands:Syntheses, Structures and Properties

Two new coordination polymers [Cu_2(bbim)(dpa)_2(C_2H_5OH)_2](1), [Co(dpa)_2(bbbm)](2)(H_2dpa = diphenic acid, bbim = 1,1?-(1,6-hexanediyl)bis-1H-benzimidazole, bbbm = 1,1?-(1,4-butanediyl)bis-1 H-benzimidazole) constructed from bis(benzimidazole)-based ligands with different lengths and diphenic acid co-ligand have been synthesized under solvothermal conditions.Complex 1 possesses Cu-dpa helical chains. The adjacent chains are connected by the bbim ligands into two-dimensional(2D) 3-connected(63) topology. Differently, the layer structure of 2 was consisted by one-dimensional chains containing alternated 8-and 18-membered rings. Furthermore,the thermal stability and fluorescence property for all crystalline materials have been investigated.

Syntheses and Crystal Structures of Two Copper(Ⅱ) Coordination Polymers Derived from Aromatic Carboxylic Acids and Bis(imidazoles)Ligands

Two compounds have been obtained by the reaction of metal（Cu（II））, 4,4＇-bis（imidazol-l-yl）diphenyl thioether（BIDPT） with two carboxylic acids, 4,4＇-oxydibenzoic acid（H2oba） and phthalic acid（H2pht）. The crystal structures of the resulting compounds, namely {[Cu（BIDPT）（oba）]·H2O}n（1） and {Cu（BIDPT）（pht）}n（2）, have been determined by single-crystal X-ray diffraction analysis. Compound 1 is of orthorhombic system, space group Pbcn with a = 27.8310（3）, b = 10.7791（1）, c = 19.3913（2）A, V = 5817.0（3） ？3 and Mr = 656.15. Compound 2 belongs to the monoclinic system, space group C2/c with a = 18.2678（2）, b = 11.0259（1）, c = 22.906（2） A, β = 97.727（2）o, V = 4571.8（8） A3 and Mr = 545.04. Structural analyses reveal that compounds 1 and 2 respectively exhibit two-dimensional（2D） wavy and corrugated layer structures. Through intermolecular hydrogen bonding, compound 1 is assembled into a 3D supramolecular structure. The thermal stability and ultraviolet spectroscopy properties of the two compounds are also investigated.

Synthesis and Crystal Structure of a New Zinc(Ⅱ)Coordination Polymer Assembled by 4-Nitrophthalic Acid and Bis(imidazol)Ligands

A new complex [Zn（4-nph）（bib）]（2n）·nH2O（1） has been obtained by the reaction of metal（Zn（Ⅱ））,1,4-bis（imidazol-1-yl）-butane（bib） with 4-nitrophthalic acid（4-H（2nph））.The crystal structure of 1 has been determined by single-crystal X-ray diffraction analysis.Compound 1 is of triclinic system,space group P1 with a = 10.3251,b = 12.4503,c = 16.6497 A,α = 88.487（3）,β = 72.529（3）,γ = 79.991（3）°,V = 2009.8（5）A^3 and Mr = 945.47.Complex 1 shows a three-dimensional（3 D） framework.Moreover,through intermolecular hydrogen bonds,compound 1 is assembled into a supramolecular structure.The thermal stability and luminescent properties of 1 are also investigated.

Synthesis and Potential Application of Novel C_(2)-Symmetrical Bis(ferrocenyl)P2N Ligand

A novel chiral bis(ferrocenyl) P2N ligand 1 with C2-symmetry was synthesized through a four-step procedure from (R)-N,N-dimethyl-1-ferrocenylethylamine. In a model reaction of Pd-catalyzed allylic alkylation of 1,3-diphenylprop-2-enyl acetate 6 with dimethyl malonate, good enantioselectivity (86% e.e.) was obtained.

Crystal Structures of Dinuclear Copper(Ⅱ) Complexesof bis (1,4,7-triazacyclononane) Ligands Containing Rigid Bridging Groups

Dinuclear Cu(Ⅱ) complexes (Cu,LCl4). 2H2O and Cu2L'Cl4 are pre-pared and characterized by X-ray structure analysis. (Cu2I-Cl4). 2H2O, C20 H40N6Cu2Cl4O2, Mr=665. 54, monoclinic, 6 for 188l observed reflections with I>3(I). Cu2L'Cl4, C20H36N6Cu2Cl4, M.=629. 41, monoclinic, for 1330 observed reflections with I>3(I). In both complexes the stereo-chemistry about Cu(Ⅱ) is 5-coordinated with two secondary amine N atoms and twoCl- occupying sites at the base of a distorted square pyramid capped by the tertiaryamine N atom. The pair of Cl' attached to the two Cu(Ⅱ) are held in anti configuration.

Two Metal-organic Coordination Polymers with Rigid Bis(triazole) Ligand： Assembly, Structures, and Fluorescence Properties

Two new coordination polymers containing rigid bis（triazole）, namely, [Ni（btb）_（0.5）（nph）（H_2O）]_n（1） and [Zn（btb）（SO_4）]_n（2）（btb = 4,4a-bis（1,2,4-triazolyl-1-yl）-biphenyl, H_2nph = 3-nitrophthalic acid） have been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a 3D trinodal（3,4,4）-connected sqc69 topology. Complex 2 presents a 2D uninodal 4-connected sql network, which is further packed into a 3D supramolecular framework by C-H···O hydrogen bonds. Thermal stabilities and fluorescence properties of two complexes have been discussed in detail.

Asymmetric Induction of Chiral 1,1'-Bis(oxazolinyl)ferrocenes as Ligands in Metal-Catalyzed Cyclopropanation and Diels-Alder Reactions

Four chiral 1,1?bis(oxazolinyl)ferrocenes(1a-1d) have been prepared and used as ligands in the copper catalyzed asymmetric cyclopropanation of styrene with ethyl diazoacetate (EDA) and the magnesium catalyzed Diels-Alder reaction between 3-acryloyl-2-oxazolidinone and cyclopentadiene. Enantioselectivities up to 24% and 41%, respectively, for cyclopropanation and Diels-Alder reaction were observed.

Two Cobalt(II) Complexes Derived from the Hydrolysis Product of Di-Schiff Base Ligand N,N'-Bis-(1-benzimidazo-2-yl-ethylidene)-ethane-1,2-diamine:Preparation,Characterization and Crystal Structure of the 6-Coordinate Species [CoL_2]X·H_2O (X = ClO_4^-, N

The reactions of Co（C1O4）2·6H2O and Co（NO3）2.6H2O with the di-Schiff base ligand N,N＇-bis-（1-benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine （LA） in ethanol have been investigated. The reactions of LA with excess amount of cobalt salts yield the six-coordinate complexes [CoL2]（ClO4）E·H2O 1 and [CoL2]（NO3）E·H2O 2 as isolatable products （L= N-（1- benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine）, where L is a tri-dentate mono-Schiff base ligand, resulting from the hydrolysis of the precursor di-Schiff base LA. Both complexes were characterized by X-ray crystallography. Crystal data for complex 1： monoclinic, space group P21/c, a = 11.9214（10）, b = 23.5828（17）, c = 14.0387（12）A, β = 135.219（4）°, C22H30Cl2CoN8O9, Mr = 680.37, V = 2780.1（4） A^3 ,Z = 4, Dc = 1.625 g/cm^3,μ（MoKa） = 0.876 mm^-1, F（000） = 1404, the final R = 0.0725 and wR = 0.1530 for 5726 observed reflections （I 〉 2σ（I））. Crystal data for complex 2： monoclinic, space group P21/c, a = 18.2162（16）, b = 10.0610（6）, c = 18.593（2）A, β = 130.099（3）°, C22H30CoN10O7, Mr = 605.49, V = 2606.5（4） A3 Z = 4, Dc = 1.543 g/cm^3,μ（MoKa） = 0.722 mm^-1, F（000） = 1260, the final R = 0.0619 and wR = 0.1429 for 5194 observed reflections （I 〉 2σ（I））. X-ray diffraction analysis reveals that each cobalt atom in the two complexes is chelated by six nitrogen atoms from two tridentate iigands L, exhibiting a slightly distorted octahedral coordination sphere. In both complexes, the strong hydrogen-bonding interactions between the lattice waters and N-H groups of the ligands result in 1D chains which are further connected by ClO4^- （or NO3^-） groups to form a 3D framework. In complex 2, the strong π-π interactions increase the stability of the structure.

基于芳基桥联双β-二亚胺配体的金属铝配合物的合成与结构表征

β-二亚胺作为一类理想的含氮单阴离子非环戊二烯基配体,可以很好的稳定低价或配位不饱和的金属配合物,而桥联的双β-二亚胺配体要比单个β-二亚胺配体多个活性位点,会以更多的方式与金属配位,该类配合物表现出更高的催化活性和更加丰富的反应性。本文利用芳基桥联双β-二亚胺配体LH_(2)(L=[μ-(1,4-C_(6)H_(4))][N(Me)CH_(2)-CH_(2)NC(Me)CC(Me)HNDipp]_(2)^(2-),Dipp=2,6-(iPr)_(2)C_(6)H_(3))和4当量的三甲基铝反应,得到了相应的双核金属铝配合物LAl_(2)Me_(4)(1)。然后通过^(1)H NMR、^(13)C{^(1)H}NMR、红外光谱和单晶X-射线衍射对该配合物进行了结构表征。

两个苯甲羟肟酸有机锡配合物的合成、结构及抗癌活性

合成了2个苯甲羟肟酸有机锡配合物:[(o-Cl-C_(6)H_(4)CH_(2))_(2)Sn(C_(6)H_(5)CONO)_(2)](1)和[(o-CH3-C_(6)H_(4)CH_(2))_(2)Sn(C_(6)H_(5)CONO)(C_(6)H_(5)COO)](2)。通过元素分析、红外光谱、核磁共振氢谱、热重分析、单晶X射线衍射等方法对配合物进行了结构表征,对其结构进行量子化学从头计算和体外抗癌活性研究。结果显示:配合物均为单锡核结构,配合物1为六配位的畸变八面体构型,配合物2为五配位的畸变三角双锥构型;配合物1对人宫颈癌细胞(HeLa)、肝癌细胞(HuH-7)和肺腺癌细胞(H1975)显示出比临床使用的顺铂强的抑制活性,而配合物2的抑制活性要弱得多。

(R,R)-环己基桥联双脒基稀土金属配合物的合成与表征

改变脒基骨架中C原子和N原子上的取代基团,可以调控脒基配体的空间位阻效应和电子效应以满足配位需求。因此,脒类化合物被广泛用作配体。手性环己基桥联双脒基配体{(R,R)-Cy-1,2-[NHCN(^(t)Bu)C_(6)H_(5)]}与离子型三胺基稀土金属配合物通过硅胺基消除反应得到了一系列结构新颖的手性环己基桥联双脒基配合物(R,R)-Cy-1,2-[NCN(tBu)C_(6)H_(5)]REN(SiMe_(3))_(2)(RE=Y(1)Er(2),Yb(3))。配合物的结构经过X-射线单晶衍射、核磁及元素分析表征,结果表明,配合物为正交晶系,空间群为P2_(1)2_(1)2_(1),配合物是由两个脒基分别以κ^(2)-N,N′,η^(1)的配位模式与金属中心成键,一个硅胺基[-N(SiMe_(3))_(2)]及一个四氢呋喃溶剂分子组成的单核五配位结构。

Aluminum Complexes Stabilized by Piperazidine-Bridged Bis（phenolate） Ligands： Syntheses, Structures, and Applica- tion in the Ring-Opening Polymerization of ε-Caprolactone

The synthesis and characterization of aluminum alkoxide and alkyl complexes stabilized by piperazidine- bridged bis（phenolate） ligands are described. Treatment of ligand precursors Hz[ONNO]^1 {Hz[ONNO]^1= 1,4-bis（2-hydroxy-3-tert-butyl-5-methylbenzyl）piperazidine} and Hz[ONNO]2 {H2[ONNO]2=1,4-bis（2-hydroxy3,5-di-tert-butylbenzyl）piperazidine} with A1Et2（OCH2Ph） and A1Etz（OPr-i）, which were generated in situ by the reactions of AIEt3 with equivalent of the corresponding alcohols, in a 1： 1 molar ratio in THF gave the corresponding aluminum alkoxide complexes [ONNO]IAI（OCH2Ph） （1） and [ONNO]2Al（OPr-i） （2）, respectively. The reaction of H2[ONNO]^1 with A1Etz（OCHzPh） in a 1 ： 2 molar ratio in THF afforded a mixture of monometallic aluminum ethyl complex [ONNO] 1A1Et （3） and complex 1, which can be isolated by stepwise crystallization. Similarly, Hz[ONNO]2 reacted with A1Etz（OPr-0 in a 1： 2 molar ratio in THF to give a mixture of aluminum ethyl complex [ONNO]2AlEt （4） and complex 2. Complexes 1 and 2 were also available via treatment of complexes 3 and 4 with 1 equiv, of benzyl alcohol and isopropyl alcohol, respectively. All of these complexes were fully characterized including X-ray structural determination. It was found that complexes 1 to 4 can initiate the ring-opening polymerization of e-caprolactone, and complexes 1 and 2 showed higher catalytic activity in comparison with com- plexes 3 and 4.

A homopolymolybdate-supported plate-like 2D cobalt network constructed from a new pyrazole-amide-pyridyl ligand: highly electrochemical activity in both capacitive performance and the detection of Cr(Ⅵ)

By employing a new semi-rigid pyrazole-amide-derived bis(pyridyl)ligand[N,N'-bis(4-picolylamine)-1-hydropyrazole(4-dpap)],a new homopolymolybdate-based two-dimensional(2D)plate-like complex[Co(4-dpap)(H_(2)O)(β-Mo_(8)O_(2)6)1/2](1)has been prepared under solvothermal condition and structurally characterized.Theβ-Mo_(8)anions are fi xed between the 2D metal–organic networks[Co(4-dpap)(H_(2)O)]n 2n+via hydrogen-bonding interaction.Complex 1 possesses satisfactory specifi c capacitance of 1512.4 F·g^(−1)(current density:1 A·g^(−1))and good cycling stability(90.8%after 1000 cycles).Moreover,1 represents a promising amperometric sensor for measurement of Cr(Ⅵ)with low detection limit(0.042μmol·L^(−1))and high durability.The insertion ofβ-Mo_(8)anions between the unique 2D metal−organic networks improves the active area of polyoxometalates,which further promotes electrochemical performance.

Binuclear Aluminum Complexes Supported by Linked Bis(β-diketiminate) Ligands for Ring-Opening Polymerization of Cyclic Esters

Binuclear aluminum alkyl complexes 2a–4g supported by linked bis（β-diketiminate） ligands were synthesized via the reaction of AlEt3 or AlMe3 and the corresponding proligand in a 2：1 molar ratio with moderate yields. The isolated complexes were well-characterized by ^1H-NMR, ^13C-NMR and elemental analysis. The binuclear nature of aluminum complex 2b was further confirmed by an X-ray diffraction study. All complexes 2a–4g could efficiently initiate the ring-opening polymerization（ROP） of ε-caprolactone in toluene. The substituents at the aromatic rings and the linker unit in the auxiliary ligands exerted significant influence on the catalytic behavior of the investigated aluminum complexes. Complex 4g（R^1 = R^2 = Cl） containing propylenyl bridging unit exhibited the highest catalytic activity among these complexes, which might be attributed to the increased electrophilicity of the metal center as well as more opened coordination sphere. The molecular weights of obtained poly（ε-caprolactone）s deviating considerably from the theoretical values indicated that the ROP of ε-caprolactone by complexes 2a–4g was not well-controlled, which was also judged from the broad molecular weight distributions（MWD = 1.47-2.47） of produced poly（ε-caprolactone）s. These complexes proved to be inactive toward the polymerization of rac-lactide alone. In the presence of alcohol the polymerization occurred, which was actually initiated by the decomposition species of the aluminum complex upon the treatment with isopropanol.

基于桥联双β-二亚胺配体的二价稀土配合物的反应性研究

金属羰基自由基配合物是有机合成与转化中重要的活性中间体,但这类配合物有不稳定和易发生偶联的缺点。为了解决这类问题,更好地发挥它的优点,金属中心和配体的的选择尤为重要。本文用桥联双β-二亚胺配体稳定的二价镱配合物L1Yb(L1=[μ-(1,2-CH_(2)CH_(2))][N(Me)CH_(2)CH_(2)NC-(Me)CHC(Me)NDipp]_(2)^(2-),Dipp=2,6-(iPr)_(2)C_(6)H_(3))与1当量二苯甲酮发生氧化还原反应,得到深紫色三价镱二苯甲酮自由基配合物L1YbOC·Ph_(2)(1),通过核磁共振氢谱、元素分析、红外光谱及单晶X-射线衍射对其结构进行了表征,发现该配合物不易发生偶联反应,具备很好的稳定性。

Syntheses of bimetallic lanthanide bis(amido) complexes stabilized by bridged bis(guanidinate) ligands and their catalytic activity toward the hydrophosphonylation reaction of aldehydes and ketones

A series of bimetallic lanthanide bis(amido) complexes stabilized by bridged bis(guanidinate) ligands {[(Me3Si)2N]2Ln[(RN)2-CN(CH2)2]}2 [R=iPr, Ln=Sm(1), Yb(2), Y(3); R=cyclohexyl(Cy), Ln=Sm(4), and Yb(5)] were synthesized through the metathesis reactions of {Ln(μ-Cl)[N(Si Me3)2]2(THF)}2(Ln=Sm, Yb, Y) with lithium guanidinate {Li[(RN)2CN(CH2)2]}2(R=iPr, Cy), the latter of which was generated in situ by the reaction of carbodiimides with lithium amides. Complexes 1–5 were well characterized by elemental analyses, IR spectra, and(for Complex 3) NMR spectroscopy. The solid-state molecular structures of all of the complexes were determined by single-crystal X-ray analyses with the exception of Complex 3, which showed similar unsolvated centrosymmetric dinuclear structures. Each of the lanthanide centers is four-coordinated with two nitrogen atoms from a guanidinate ligand and two nitrogen atoms from two amido groups. The piperazidine rings adopt chair conformations in all cases. These organolanthanide complexes were found to be efficient catalysts for the hydrophosphonylation reaction of various aldehydes and unactivated ketones and to afford ?-hydroxyphosphonates in high yields under low catalyst loading(0.1 mol%) in a short reaction time.

Two Novel Cobalt(Ⅱ)/nickel(Ⅱ) Metal-organic Coordination Polymers Based on Flexible Polycarboxylic Acids and Rigid Bis(imidazole) Mix Ligands

Two novel metal-organic coordination compounds, [Co2(OH)(chdc)1.5(bibp)]n(1) and [Ni(chdc)(bib)]n·2nH2O(2, H2chdc=1,4-cyclohexanedicarboxylic acid, bibp=4,4’-bis(1-imidazolyl)biphenyl, bib=1,4-bis(1-imidazolyl)benzene), were synthesized and characterized. Compound 1 crystallizes in monoclinic system, space group PI with a=10.591(3), b=11.146(3), c=12.264(3) ?, α=89.009(6), β=88.397(4), γ=87.823(3)°, V=1446.0(6) ?3, Dc=1.554 g/cm3, C30H30Co2N4O7, Mr=676.44, F(000)=696, μ(MoKα)=1.202 mm-1, Z=2, R=0.0278 and wR=0.0718. In 1, it contains an interesting tetranuclear Co(Ⅱ) cluster. The neighboring {Co4} clusters are linked by chdc2-ligands to generate a 2D network. The bibp ligands connect adjacent layers to form an open 3 D metal-organic framework. Compound 2 crystallizes in monoclinic system, space group P21/n with a=8.8110(1), b=19.369(1), c=12.7379(4) ?, β=102.952(5)o, V=2118.5(2) ?3, Dc=1.490 g/cm3, C20H24N4NiO6, Mr=475.14, F(000)=992, μ(MoKα)=0.961 mm-1, Z=4, R=0.0306 and wR=0.0738. In 2, each deprotonated chdc 2-ligand links two Ni(Ⅱ) atoms to generate a 1 D chain along the a axis. The adjacent chains are further connected by bib ligands to build up an interesting two-dimensional network. Compound 1 shows antiferromagnetic property.